Olefin oligomerizations using chemically-treated solid oxides

ABSTRACT

The present invention discloses processes for oligomerizing a monomer containing C3 to C30 olefins using a chemically-treated solid oxide, such as fluorided silica-coated alumina and fluorided-chlorided silica-coated alumina.

REFERENCE TO RELATED APPLICATION

This application is a divisional application of co-pending U.S. patentapplication Ser. No. 14/977,728, filed on Dec. 22, 2015, now U.S. Pat.No. 9,890,093, the disclosure of which is incorporated herein byreference in its entirety.

This application is a divisional application of co-pending U.S. patentapplication Ser. No. 14/977,728, filed on Dec. 22, 2015, now U.S. Pat.No. 9,890,093, the disclosure of which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION

The present invention relates generally to processes for oligomerizingolefins using a chemically-treated solid oxide. In certainoligomerization processes, the chemically-treated solid oxide cancomprise fluorided silica-coated alumina or fluorided-chloridedsilica-coated alumina.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described herein. This summary is notintended to identify required or essential features of the claimedsubject matter. Nor is this summary intended to be used to limit thescope of the claimed subject matter.

Processes for oligomerizing olefins are disclosed and described herein.Such processes can comprise (i) introducing a monomer comprising a C₃ toC₃₀ olefin and a chemically-treated solid oxide into a reaction zone,and (ii) oligomerizing the monomer to form an oligomer product in thereaction zone. In some embodiments, the monomer can comprise a C₃ to C₁₂alpha olefin (or normal alpha olefin) and the chemically-treated solidoxide can comprise fluorided silica-coated alumina, fluorided-chloridedsilica-coated alumina, or sulfated alumina. These processes can provideunexpectedly high olefin conversions and desirable selectivity tovarious oligomer product fractions (e.g., dimers or trimers).

Polyalphaolefins (PAO's) also are disclosed and described herein. In anembodiment of this invention, the PAO's can be characterized by aviscosity index greater than or equal to 110 and a kinematic viscosityat −40° C. of less than or equal to 1750 cSt. The PAO's can comprise C₂₄saturated hydrocarbons, or can comprise hydrogenated oligomers of a C₆to C₁₂ olefin, but are not limited thereto.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter can be described such that,within particular aspects and/or embodiments, a combination of differentfeatures can be envisioned. For each and every aspect, and/orembodiment, and/or feature disclosed herein, all combinations that donot detrimentally affect the designs, compositions, processes, and/ormethods described herein are contemplated with or without explicitdescription of the particular combination. Additionally, unlessexplicitly recited otherwise, any aspect, and/or embodiment, and/orfeature disclosed herein can be combined to describe inventive featuresconsistent with the present disclosure.

Regarding claim transitional terms or phrases, the transitional term“comprising,” which is synonymous with “including,” “containing,”“having,” or “characterized by,” is open-ended and does not excludeadditional, unrecited elements or method steps. The transitional phrase“consisting of” excludes any element, step, or ingredient not specifiedin the claim. The transitional phrase “consisting essentially of” limitsthe scope of a claim to the specified materials or steps and those thatdo not materially affect the basic and novel characteristics of theclaimed invention. A “consisting essentially of” claim occupies a middleground between closed claims that are written in a “consisting of”format and fully open claims that are drafted in a “comprising” format.Absent an indication to the contrary, describing a composition or methodas “consisting essentially of” is not to be construed as “comprising,”but is intended to describe the recited element that includes materialsor steps which do not significantly alter the composition or method towhich the term is applied. For example, a monomer consisting essentiallyof a material A can include impurities typically present in acommercially produced or commercially available sample of the recitedcompound or composition. When a claim includes different features and/orfeature classes (for example, a method step, monomer features, and/orproduct features, among other possibilities), the transitional termscomprising, consisting essentially of, and consisting of apply only tothe feature class to which it is utilized, and it is possible to havedifferent transitional terms or phrases utilized with different featureswithin a claim. For example, a method can comprise several recited steps(and other non-recited steps), but utilize a monomer consisting ofspecific components; alternatively, consisting essentially of specificcomponents; or alternatively, comprising the specific components andother non-recited components. While compositions and methods aredescribed in terms of “comprising” various components or steps, thecompositions and methods can also “consist essentially of” or “consistof” the various components or steps, unless specifically statedotherwise. For example, a chemically-treated solid oxide consistent withcertain embodiments of the present invention can comprise;alternatively, consist essentially of; or alternatively, consist of; afluorided solid oxide.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an electron-withdrawing anion” is meant toencompass one, or combinations of more than one, electron-withdrawinganion (e.g., sulfate, chloride, fluoride, etc.), unless otherwisespecified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound or group disclosed herein, any name orstructure presented is intended to encompass all conformational isomers,regioisomers, stereoisomers, and mixtures thereof that can arise from aparticular set of substituents, unless otherwise specified. The name orstructure also encompasses all enantiomers, diastereomers, and otheroptical isomers (if there are any), whether in enantiomeric or racemicforms, as well as mixtures of stereoisomers, as would be recognized by askilled artisan, unless otherwise specified. For example, a generalreference to hexene (or hexenes) includes all linear or branched,acyclic or cyclic, hydrocarbon compounds having six carbon atoms and 1carbon-carbon double bond; a general reference to pentane includesn-pentane, 2-methyl-butane, and 2,2-dimethylpropane; a general referenceto a butyl group includes an n-butyl group, a sec-butyl group, aniso-butyl group, and a t-butyl group; a general reference tocyclododecatriene includes all isomeric forms (e.g.,trans,trans,cis-1,5,9-cyclododecatriene, andtrans,trans,trans-1,5,9-cyclododecatriene, among other dodecatrienes);and a general reference to 2,3-pentanediol includes 2R,3R-pentanediol,2S,3S-pentanediol, 2R,3S-pentanediol, and mixtures thereof.

The terms “contact product,” “contacting,” and the like, are used hereinto describe compositions and methods wherein the components arecontacted together in any order, in any manner, and for any length oftime, unless otherwise specified. For example, the components can becontacted by blending or mixing. Further, unless otherwise specified,the contacting of any component can occur in the presence or absence ofany other component of the compositions and methods described herein.Combining additional materials or components can be done by any suitablemethod. Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can, and often does, includereaction products, it is not required for the respective components toreact with one another. Similarly, the term “contacting” is used hereinto refer to materials which can be blended, mixed, slurried, dissolved,reacted, treated, or otherwise contacted in some other manner. Hence,“contacting” two or more components can result in a mixture, a reactionproduct, a reaction mixture, etc.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. The term“olefin” as used herein refers to a hydrocarbon that has at least onecarbon-carbon double bond that is not part of an aromatic ring or ringsystem. The term “olefin” includes aliphatic and aromatic, cyclic andacyclic, and/or linear and branched compounds having at least onecarbon-carbon double bond that is not part of an aromatic ring or ringsystem, unless specifically stated otherwise. Olefins having only one,only two, only three, etc., carbon-carbon double bonds can be identifiedby use of the term “mono,” “di,” “tri,” etc., within the name of theolefin. The olefins can be further identified by the position of thecarbon-carbon double bond(s). The term “alpha olefin” as used hereinrefers to any olefin that has a double bond between the first and secondcarbon atom of a contiguous chain of carbon atoms. The term “alphaolefin” includes linear and branched alpha olefins and alpha olefinswhich have more than one non-aromatic carbon-carbon double bond, unlessexpressly stated otherwise. The term “normal alpha olefin” as usedherein refers to a linear hydrocarbon mono-olefin having a double bondbetween the first and second carbon atom.

A “polyalphaolefin” (PAO) is a mixture of hydrogenated (oralternatively, substantially saturated) oligomers, containing unitsderived from an alpha olefin monomer. Unless specified otherwise, thePAO can contain units derived from alpha olefin monomer units, which canbe the same (hydrogenated or substantially saturated alpha olefinhomo-oligomer) or can be different (hydrogenated or substantiallysaturated alpha olefin co-oligomer). One having ordinary skill in theart will recognize that depending on the process utilized to produce thePAO, the as-produced alpha olefin oligomers can already be substantiallysaturated. For example, a process which is carried out in the presenceof hydrogen can produce an olefin oligomer which may or may not requirea separate hydrogenation step to provide a product with the desiredproperties.

The term “oligomerization,” and its derivatives, refers to processeswhich produce a mixture of products containing from 2 to 60 olefinmonomer units. An “oligomer” is a molecule that contains from 2 to 60olefin monomer units (per molecule) and an “oligomerization product” or“oligomer product” includes all products made by the “oligomerization”process, including the “oligomers” and products which are not“oligomers” (e.g., products which contain more than 60 monomer units),but excludes non-oligomerized olefin monomer (excludes residualunreacted monomer). It should be noted that the monomer units in the“oligomer” or “oligomerization product” do not have to be the same. Forexample, these terms are also used generically herein to include olefinhomo-oligomers, co-oligomers, and so forth, and thus encompass productsderived from any number of different olefin monomers disclosed herein.In like manner, oligomerizing (or oligomerization) is meant toencompasses dimerizing (or dimerization), trimerizing (ortrimerization), and so forth.

Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of theinvention, the typical methods and materials are herein described.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

DETAILED DESCRIPTION OF THE INVENTION

The oligomerization of monomers comprising a C₃ to C₃₀ olefin using achemically-treated solid oxide are disclosed herein. Also disclosedherein are polyalphaolefins (PAO's) having a combination of a highviscosity index and a reduced viscosity at low temperatures (e.g.,kinematic viscosity at −40° C.).

Olefin Oligomerizations Processes

Embodiments of this invention are directed to processes for forming anoligomer product. Such oligomerization processes can comprise (orconsist essentially of, or consist of) (i) introducing a monomercomprising olefins and a chemically-treated solid oxide into a reactionzone, and (ii) oligomerizing the monomer to form the oligomer product inthe reaction zone; or alternatively, (i) introducing a monomercomprising a C₃ to C₃₀ olefin and a chemically-treated solid oxide intoa reaction zone, and (ii) oligomerizing the monomer to form the oligomerproduct in the reaction zone.

Generally, the features of the processes (e.g., the components and/orfeatures of the monomer, the olefins (e.g., carbon number and/or olefintype, among other olefin features) of the monomer, thechemically-treated solid oxide, and the conditions under which theoligomer product is formed, among others) are independently describedherein and these features can be combined in any combination to furtherdescribe the disclosed oligomerization processes. Moreover, additionalprocess steps can be performed before, during, and/or after any of thesteps of any of the processes disclosed herein, and can be utilizedwithout limitation and in any combination to further describe theoligomerization process, unless stated otherwise.

In some embodiments, the monomer can comprise, consist essentially of,of consist of, C₃ to C₃₀ olefins. Moreover, the monomer can comprise,consist essentially of, or consist of, any single carbon number olefinsfrom C₃ to C₃₀ (e.g., C₆ olefins) or any combination of different singlecarbon number olefins from C₃ to C₃₀ (e.g., C₃ to C₆ olefins, or C₈,C₁₀, and C₁₂ olefins, among other combinations). Monomers and olefinsare described herein and their features can be utilized withoutlimitation to further describe the monomer and olefins which can beutilized in the oligomerization processes. In some embodiments, anoligomerization process can utilize a single chemically-treated solidoxide; or alternatively, the process can utilize more than onechemically-treated solid oxide. Chemically-treated solid oxides aredescribed herein and can be utilized without limitation in theoligomerization processes described herein.

In some embodiments, the introducing step of the process can includeadding the monomer, the chemically-treated solid oxide, and additionalunrecited materials (e.g., a non-olefin solvent or diluent, astabilizer, amongst other materials) into a reaction zone. In otherembodiments, the introducing step can consist essentially of adding themonomer and the chemically-treated solid oxide into the reaction zoneor, alternatively, consist of adding the monomer and thechemically-treated solid oxide into the reaction zone. Likewise,additional materials or features can be employed in the oligomerizingstep. For instance, the formation of the oligomer product in thereaction zone can occur in the presence of a non-olefin solvent. Theamount of any non-olefin solvent used in addition to the disclosedolefins of the monomer in the introducing step and/or the oligomerizingstep of the process is not limited to any particular range. Suchsolvent, or combination of solvents, can be used, for example, as a flowmodifier to alter the flow properties or viscosity of the reaction zonemixture including the monomer (or olefin) and/or the oligomer product.Non-olefin solvents which can be utilized are described herein, andthese solvents can be utilized without limitation in the oligomerizationprocesses described herein. In an embodiment, the oligomerization stepcan be performed in the substantial absence of a solvent (e.g., lessthan 10, 5, 4, 3, 2, or 1 wt. % solvent, based upon the total weight ofthe monomer and the solvent).

Independently, the introducing step and the oligomerizing step of theprocess for forming an oligomer product can be conducted at a variety oftemperatures, pressures, and time periods. For instance, the temperatureat which the monomer and the chemically-treated solid oxide areintroduced into the reaction zone can be the same as, or different from,the temperature at which the oligomer product is formed. As anillustrative example, in the introducing step, the monomer and thechemically-treated solid oxide can be fed into a reaction zone attemperature T1 and, after this initial charging of these materials, thetemperature can be changed to a temperature T2 to allow for theoligomerizing of the monomer to form the oligomer product. Likewise, thepressure can be different in the introducing step than in theoligomerizing step. Often, the time period in the introducing step canbe referred to as the charging time, while the time period in theoligomerizing step can be referred to as the reaction time. The chargingtime and the reaction time can be, and often are, different.

In an embodiment, the introducing step and/or the oligomerizing step ofthe process for forming an oligomer product can be conducted at anysuitable temperature for the monomer and the chemically-treated solidoxide. For instance, the introducing step and/or the oligomerizing stepcan be conducted at a minimum temperature of 0° C., 10° C., 15° C., or20° C.; or alternatively, at a maximum temperature of 250° C., 225° C.,200° C., 180° C., or 150° C. In an embodiment, the introducing stepand/or the oligomerizing step can be conducted at a temperature in arange from any minimum temperature disclosed herein to any maximumtemperature disclosed herein. In some non-limiting embodiments, theintroducing step and/or the oligomerizing step can be conducted attemperature in a range from 0° C. to 250° C.; alternatively, from 0° C.to 200° C.; alternatively, from 10° C. to 250° C.; alternatively, from10° C. to 225° C.; alternatively, from 15° C. to 225° C.; alternatively,from 15° C. to 200° C.; or alternatively, from 15° C. to 180° C. Inother non-limiting embodiments, the contacting step and/or theoligomerizing step can be conducted at a temperature in a range from 10°C. to 200° C., from 20° C. to 200° C., from 20° C. to 180° C., or from20° C. to 150° C. Other temperature ranges for the introducing stepand/or the oligomerizing step are readily apparent from this disclosure.These temperature ranges also are meant to encompass circumstances whereeither the introducing step, the oligomerizing step, or both, can beconducted at a series of different temperatures, instead of at a singlefixed temperature, falling within the respective temperature ranges.

Generally, the oligomerization can be performed at any suitablepressure. While not being limited thereto, the introducing step and/orthe oligomerizing step of the process for forming an oligomer productcan be conducted at a reactor pressure in a range from 0 to 1000 psig,from 5 to 1000 psig, from 5 to 750 psig, from 5 to 500 psig, from 5 to250 psig, from 5 to 150 psig, or from 10 to 100 psig. In someembodiments, the introducing step and/or the oligomerizing step can beconducted at atmospheric pressure, while in other embodiments, theintroducing step and/or the oligomerizing step can be conducted atsub-atmospheric pressures.

In the oligomerization process, the weight ratio of the monomer to thechemically-treated solid oxide is not particularly limited. In someembodiments, however, the weight ratio can be in a range from 1:1 to1000:1, from 1:1 to 100:1, or from 2:1 to 1000:1. In other embodiments,the weight ratio can be in a range from 2:1 to 100:1, from 5:1 to1000:1, or from 5:1 to 100:1. Other weight ratios of the monomer to thechemically-treated solid oxide are readily apparent from thisdisclosure.

Often, the process for forming the oligomer product can be a flowprocess and/or a continuous process (e.g., a fixed bed reactor process).In such circumstances, the monomer and chemically-treated solid oxidecontact time (or reaction time) can be expressed in terms of weighthourly space velocity (WHSV)—the ratio of the weight of the monomerwhich comes in contact with a given weight of chemically-treated solidoxide per unit time (units of g/g/hr). While not limited thereto, theWHSV employed for the process of producing an oligomer product can havea minimum value of 0.05, 0.1, 0.25, 0.5, 0.75, or 1; or alternatively, amaximum value of 5, 4, 3, 2.5, or 2. In an embodiment, the WHSV can bein a range from any minimum WHSV disclosed herein to any maximum WHSVdisclosed herein. In a non-limiting example, the WHSV can be in a rangefrom 0.05 to 5; alternatively, from 0.05 to 4; alternatively, from 0.1to 5; alternatively, from 0.1 to 4; alternatively, from 0.1 to 3;alternatively, from 0.1 to 2; alternatively, from 0.1 to 1;alternatively, from 0.1 to 0.8; alternatively, from 0.5 to 5;alternatively, from 0.5 to 4; alternatively, from 0.5 to 2.5;alternatively, from 0.8 to 3; or alternatively, from 1 to 3. Other WHSVranges are readily apparent from this disclosure.

The reaction zone can comprise any suitable reactor or vessel in orderto form the oligomer product, non-limiting examples of which can includea fixed bed reactor, a stirred tank reactor, a plug flow reactor, and atubular reactor, including more than one reactor in series or inparallel, and including any combination of reactor types andarrangements. The oligomerization process disclosed herein can be abatch process in some embodiments, while in other embodiments, theoligomerization process can be a continuous process.

In an embodiment, the minimum monomer conversion (or olefin conversion)can be at least 10%, by weight percent or by mole percent. Theconversion of the monomer can be described as a “monomer conversion” toindicate that the percentage conversion, in weight percent or in molepercent, is based on the monomer and does not include non-monomermaterials that can be present (e.g., solvent, etc.) during theoligomerization. Likewise, for example, the conversion of a monomer (orolefin conversion) comprising a C₆ olefin can be described as a “C₆olefin conversion” to indicate that the percentage conversion, in weightpercent or in mole percent, is based on the C₆ olefin and does notinclude non-C₆ olefin materials that can be present (e.g., solvent,other carbon number olefins, etc.) during the oligomerization. Inanother embodiment, the minimum monomer conversion (or olefinconversion) can be at least 15%, at least 20%, at least 25%, at least30%, at least 40%, or at least 50%, and these percentages can be weightpercentages or mole percentages. In yet another embodiment, the maximummonomer conversion (or olefin conversion) can be 100%, 95%, 90%, 85%,80%, 75%, 70%, 65%, 60%, or 55%, and these percentages can be weightpercentages or mole percentages. Generally, the monomer conversion (orolefin conversion) can be in a range from any minimum conversiondisclosed herein to any maximum conversion disclosed herein.Non-limiting ranges of monomer conversion (or olefin conversion), inweight or mole percentages, can include, but are not limited to, thefollowing ranges: from 10% to 95%, from 10% to 85%, from 10% to 75%,from 10% to 60%, from 15% to 90%, from 15% to 75%, from 20% to 90%, from20% to 75%, from 30% to 85%, from 30% to 75%, from 40% to 95%, from 40%to 80%, or from 40% to 75%. Other monomer conversion (or olefinconversion) ranges are readily apparent from this disclosure. In someembodiments, these conversions can be achieved in a batch process, whilein other embodiments, these conversions can be achieved in a flow orcontinuous process, such as, for example, multi-passes thru a reactor,such as a fixed bed reactor. Yet, in other embodiments, theseconversions can be achieved in a flow or continuous process, such as,for example, a single pass thru a reactor, such as a fixed bed reactor.In such embodiments, the conversions can be described as “single passconversions” to indicate that the percentage conversions, in weightpercent or in mole percent, are based on a single pass thru a reactor orreaction zone.

In an oligomerization process consistent with this invention in whichthe chemically-treated solid oxide comprises fluorided silica-coatedalumina, unexpectedly, a conversion (or single pass conversion) of themonomer to the oligomer product is greater than that of a comparableprocess using sulfated alumina (i.e., instead of fluorided silica-coatedalumina), under the same oligomerization conditions. In particularembodiments, the increase in conversion using fluorided silica-coatedalumina instead of sulfated alumina can be at least 10%, at least 20%,at least 30%, at least 40%, at least 50%, at least 75%, or at least100%, and often up to 150-200%. The percentage increases are based onthe conversion using sulfated alumina; for example, if the conversionusing sulfated alumina (in weight or mole percentage) was 20% and theconversion using fluorided silica-coated alumina (in the same weight ormole percentage basis as the sulfated alumina) was 30%, then thepercentage increase would be a 50% increase.

Similarly, in an oligomerization process consistent with this inventionin which the chemically-treated solid oxide comprisesfluorided-chlorided silica-coated alumina, unexpectedly, a conversion(or single pass conversion) of the monomer (comprising the C₃ to C₃₀olefin, or comprising any single carbon number olefins, or comprisingany combination of different single carbon number olefins, etc.) to theoligomer product is greater than that of a comparable process usingsulfated alumina (i.e., instead of fluorided-chlorided silica-coatedalumina), under the same oligomerization conditions. In particularembodiments, the increase in conversion using fluorided-chloridedsilica-coated alumina instead of sulfated alumina can be at least 10%,at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, orat least 100%, and often up to 150-200%. The percentage increases arebased on the conversion using sulfated alumina; for example, if theconversion using sulfated alumina (in weight or mole percentage) was 20%and the conversion using fluorided-chlorided silica-coated alumina (inthe same weight or mole percentage basis as the sulfated alumina) was25%, then the percentage increase would be a 25% increase.

Monomers Containing Olefins

Embodiments of this invention are directed to processes comprisingintroducing a monomer comprising a C₃ to C₃₀ olefin and achemically-treated solid oxide into a reaction zone, and oligomerizingthe monomer to form an oligomer product in the reaction zone. A widerange of monomers comprising, consisting essentially of, or consistingof, C₃ to C₃₀ olefins can be oligomerized according to the methodsprovided herein, and using the chemically-treated solid oxides disclosedherein. In any embodiment, the monomer can comprise internal olefinsand/or the monomer can comprise alpha olefins. Further, the alphaolefins can comprise, or consist essentially of, normal alpha olefins.Consequently, in some embodiments, the oligomerization processesdisclosed herein can employ a monomer which is a mixture of internalolefins and alpha olefins. In particular embodiments, the monomer cancomprise, or consist essentially of, normal alpha olefins.

Generally, the monomer can comprise (or consist essentially of, orconsist of) C₃ to C₃₀ olefins, or alternatively, C₃ to C₁₈ olefins. Inone embodiment, the monomer can comprise (or consist essentially of, orconsist of) C₃ to C₅ olefins, while in another embodiment, the monomercan comprise (or consist essentially of, or consist of) C₆ to C₁₈olefins, or C₈ to C₁₂ olefins. In yet another embodiment, the monomercan comprise C₃ to C₈ olefins, C₁₀ to C₁₈ olefins, C₆ to C₁₆ olefins, orC₁₂ to C₁₆ olefins. In other embodiments, the monomer can comprise (orconsist essentially of, or consist of) C₃ olefins; alternatively, C₆olefins; alternatively, C₈ olefins; alternatively, C₁₀ olefins;alternatively, C₁₂ olefins; alternatively, C₁₄ olefins; alternatively,C₁₆ olefins; or alternatively, C₁₈ olefins. Thus, mixtures of olefinshaving different numbers of carbon atoms can be used, or olefins havingpredominantly a single number of carbon atoms can be used as themonomer.

In an embodiment, the monomer can comprise at least 50 wt. %, at least55 wt. %, at least 60 wt. %, at least 65 wt. %, at least 70 wt. %, atleast 75 wt. %, at least 80 wt. %, at least 85 wt. %, at least 90 wt. %,at least 92.5 wt. %, or at least 95 wt. % of any olefin, olefin carbonnumber range, or mixture of olefins described herein. Additionally oralternatively, the monomer can comprise a maximum of 100 wt. %, 99 wt.%, 98 wt. %, 97 wt. %, or 96 wt. %, of any olefin, olefin carbon numberrange, or mixture of olefins described herein. Generally, the weightpercent can be in a range from any minimum weight percent disclosedherein to any maximum weight percent disclosed herein. Therefore,non-limiting monomer weight percent ranges can include, but are notlimited to, the following ranges: from 50 to 100 wt. %, from 55 to 99wt. %, from 60 to 98 wt. %, from 65 to 97 wt. %, from 70 to 96 wt. %,from 75 to 100 wt. %, from 80 to 100 wt. %, or from 80 to 98 wt. % ofany olefin, olefin carbon number range, or mixture of olefins describedherein. Other monomer weight percent ranges are readily apparent fromthis disclosure.

In these and other embodiments, the olefins can be cyclic or acyclic,and/or linear or branched. For example, the monomer can comprise,consist essentially of, or consist of, cyclic olefins; additionally oralternatively, the monomer can comprise, consist essentially of, orconsist of, linear olefins. Moreover, the monomer can comprise olefinshaving only one olefin moiety (mono-olefins) and/or olefins having twoolefin moieties (di-olefins), as well as compounds having more than twoolefin moieties per molecule; alternatively, mono-olefins;alternatively, di-olefins; or alternatively, olefins having more thantwo olefin moieties per molecule.

The monomer can comprise linear and/or branched olefins, and therefore,mixtures of linear and branched olefins can be used. Suitable branchedolefins can, for example, have a branch at any position and can have thedouble bond at any suitable position. In one embodiment, the branchedolefin can have more than one branch. In another embodiment, thebranched olefin can have one or more branches at the carbon-carbondouble bond; or alternatively, the branched olefin can have one or morebranches on carbon atoms that are not part of a carbon-carbon doublebond. In yet another embodiment, the olefins can comprise, consistessentially of, or consist of, linear olefins.

In further embodiments, the monomer can comprise (or consist essentiallyof, or consist of) C₃ to C₃₀ alpha olefins (or normal alpha olefins), oralternatively, C₃ to C₁₈ alpha olefins (or normal alpha olefins). In oneembodiment, for example, the monomer can comprise (or consistessentially of, or consist of) C₃ to C₅ alpha olefins (or normal alphaolefins), while in another embodiment, the monomer can comprise (orconsist essentially of, or consist of) C₆ to C₁₈ alpha olefins (ornormal alpha olefins), or C₈ to C₁₂ alpha olefins (or normal alphaolefins). In yet another embodiment, the monomer can comprise C₃ to C₈alpha olefins (or normal alpha olefins), C₁₀ to C₁₈ alpha olefins (ornormal alpha olefins), C₆ to C₁₆ alpha olefins (or normal alphaolefins), or C₁₂ to C₁₆ alpha olefins (or normal alpha olefins). Inother embodiments, the monomer can comprise (or consist essentially of,or consist of) propylene, 1-butene, 1-pentene, or any combinationthereof; alternatively, propylene; alternatively, 1-butene; oralternatively, 1-pentene. Yet, in other embodiments, the monomer cancomprise (or consist essentially of, or consist of) 1-hexene, 1-octene,1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or any combinationthereof; alternatively, 1-octene, 1-decene, 1-dodecene, or anycombination thereof; alternatively, 1-hexene; alternatively, 1-octene;alternatively, 1-decene, alternatively, 1-dodecene; alternatively,1-tetradecene; or alternatively, 1-hexadecene. Thus, mixtures of alphaolefins (or normal alpha olefins) having different numbers of carbonatoms can be used, or alpha olefins (or normal alpha olefins) havingpredominantly a single number of carbon atoms can be used as themonomer.

Moreover, as above, the monomer can contain any suitable amount of anyolefin, olefin carbon number range, or mixture of olefins describedherein. For instance, the monomer can contain from 50 to 100 wt. %, from55 to 99 wt. %, from 60 to 98 wt. %, from 65 to 97 wt. %, from 70 to 96wt. %, from 75 to 100 wt. %, from 80 to 100 wt. %, or from 80 to 98 wt.% C₃ to C₃₀ alpha olefins (or normal alpha olefins); alternatively,alpha olefins (or normal alpha olefins) of any carbon number rangedescribed herein; alternatively, of any combination of single carbonnumbered alpha olefins (and/or normal alpha olefins) described herein;or alternatively, of any single carbon numbered alpha olefins (or normalalpha olefins) described herein. Additionally, other monomer weightpercent ranges are readily apparent from this disclosure. For instance,in a non-limiting example, the monomer can comprise can comprise atleast 75 wt. %, at least 80 wt. %, at least 85 wt. %, at least 90 wt. %,or at least 95 wt. %, of propylene; alternatively, 1-hexene;alternatively, 1-octene; alternatively, 1-decene; alternatively,1-dodecene; alternatively, 1-tetradecene; or alternatively,1-hexadecene.

As described herein, the monomer can comprise various carbon numberranges and/or types of olefins. The various carbon numbers of theolefin(s), the type of olefin(s), and the weight percentage of theolefin(s) can be combined in any fashion to describe the monomer orolefin(s) that can be used in the oligomerization processes of thisinvention.

Chemically-Treated Solid Oxides

In the processes disclosed herein, a monomer and a chemically-treatedsolid oxide can be introduced into a reaction zone, and the monomer canbe oligomerized to form an oligomer product in the reaction zone. Anysuitable chemically-treated solid oxide can be employed in thisinvention, whether one chemically-treated solid oxide or a mixture orcombination of two or more different chemically-treated solid oxides. Inaccordance with particular embodiments of this invention, theoligomerizing step can be conducted in the substantial absence oforganoaluminum compounds, metallocene compounds, or both organoaluminumand metallocene compounds (e.g., less than 5, 4, 3, 2, 1, or 0.5 wt. %organoaluminum compounds, metallocene compounds, or both organoaluminumand metallocene compounds, based upon the weight of thechemically-treated solid oxide).

In one embodiment, the chemically-treated solid oxide can comprise asolid oxide treated with an electron-withdrawing anion. Alternatively,in another embodiment, the chemically-treated solid oxide can comprise asolid oxide treated with an electron-withdrawing anion, the solid oxidecontaining a Lewis-acidic metal ion. Non-limiting examples of suitablechemically-treated solid oxides are disclosed in, for instance, U.S.Pat. Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973,8,703,886, and 9,023,959.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form a chemically-treated solid oxide,either singly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, and titania-zirconia. The solid oxide usedherein also can encompass oxide materials such as silica-coated alumina,as described in U.S. Pat. No. 7,884,163.

Accordingly, in one embodiment, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, silica-titania,zirconia, silica-zirconia, magnesia, boria, zinc oxide, any mixed oxidethereof, or any combination thereof. In another embodiment, the solidoxide can comprise alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,silica-titania, zirconia, silica-zirconia, magnesia, boria, or zincoxide, as well as any mixed oxide thereof, or any mixture thereof. Inanother embodiment, the solid oxide can comprise silica, alumina,titania, zirconia, magnesia, boria, zinc oxide, any mixed oxide thereof,or any combination thereof. In yet another embodiment, the solid oxidecan comprise silica-alumina, silica-coated alumina, silica-titania,silica-zirconia, alumina-boria, or any combination thereof. In stillanother embodiment, the solid oxide can comprise silica, alumina,silica-alumina, silica-coated alumina, or any mixture thereof;alternatively, silica; alternatively, alumina; alternatively,silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have a silica content from 5 to 95% by weight. In oneembodiment, the silica content of these solid oxides can be from 10 to80%, or from 20% to 70%, silica by weight. In another embodiment, suchmaterials can have silica contents ranging from 15% to 60%, from 25% to50%, from 25% to 48%, or from 20% to 45%, silica by weight. The solidoxides contemplated herein can have any suitable surface area, porevolume, and particle size, as would be recognized by those of skill inthe art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to oneembodiment, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, tungstate, and molybdate, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsalso can be employed. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, or any combination thereof, in someembodiments provided herein. In other embodiments, theelectron-withdrawing anion can comprise sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, or combinations thereof. Yet, in other embodiments, theelectron-withdrawing anion can comprise sulfate, fluoride, chloride, orcombinations thereof; alternatively, sulfate; alternatively, fluorideand chloride; or alternatively, fluoride.

The chemically-treated solid oxide generally can contain from 1 to 25wt. % of the electron-withdrawing anion, based on the weight of thechemically-treated solid oxide. In particular embodiments providedherein, the chemically-treated solid oxide can contain from 1 to 20 wt.%, from 2 to 20 wt. %, from 3 to 20 wt. %, from 2 to 15 wt. %, from 3 to15 wt. %, from 3 to 12 wt. %, or from 4 to 10 wt. %, of theelectron-withdrawing anion, based on the total weight of thechemically-treated solid oxide.

In an embodiment, the chemically-treated solid oxide can comprisefluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, fluorided-chlorided silica-coated alumina, sulfatedsilica-coated alumina, or phosphated silica-coated alumina, as well asany mixture or combination thereof. In another embodiment, thechemically-treated solid oxide employed herein can be, or can comprise,a fluorided solid oxide and/or a sulfated solid oxide, non-limitingexamples of which can include fluorided alumina, sulfated alumina,fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, fluorided silica-coated alumina, fluorided-chloridedsilica-coated alumina, or sulfated silica-coated alumina, as well ascombinations thereof. In yet another embodiment, the chemically-treatedsolid oxide can comprise fluorided alumina; alternatively, chloridedalumina; alternatively, sulfated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,fluorided silica-zirconia; alternatively, chlorided silica-zirconia;alternatively, sulfated silica-coated alumina; alternatively,fluorided-chlorided silica-coated alumina; or alternatively, fluoridedsilica-coated alumina. In some embodiments, the chemically-treated solidoxide can comprise a fluorided solid oxide, while in other embodiments,the chemically-treated solid oxide can comprise a sulfated solid oxide.

Various processes can be used to form chemically-treated solid oxidesuseful in the present invention. Methods of contacting the solid oxidewith the electron-withdrawing component, suitable electron withdrawingcomponents and addition amounts, impregnation with metals or metal ions(e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, or combinations thereof), and variouscalcining procedures and conditions are disclosed in, for example, U.S.Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553,6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987,6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274,6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485. Othersuitable processes and procedures for preparing chemically-treated solidoxides (e.g., fluorided solid oxides, sulfated solid oxides, etc.) arewell known to those of skill in the art.

Non-Olefin Solvents

Illustrative non-olefin organic solvents which can be utilized in theprocesses disclosed herein can include aliphatic hydrocarbons, petroleumdistillates, or combinations thereof; alternatively, aliphatichydrocarbons; or alternatively, petroleum distillates. Generally,suitable solvents include solvents that do not react with the monomers,olefins, alpha olefins, etc., disclosed herein. In an embodiment, anysolvent described herein can be substantially devoid of water (e.g.,less than 100, 75, 50, 25, 10, 5, or 1 ppm water by weight).

Aliphatic hydrocarbons which can be useful as an oligomerization solventinclude C₃ to C₂₀ aliphatic hydrocarbons; alternatively C₄ to C₁₅aliphatic hydrocarbons; or alternatively, C₅ to C₁₀ aliphatichydrocarbons. The aliphatic hydrocarbons can be cyclic or acyclic and/orcan be linear or branched, unless otherwise specified.

Non-limiting examples of suitable acyclic aliphatic hydrocarbon solventsthat can be utilized singly or in any combination include pentane(n-pentane or a mixture of linear and branched C₅ acyclic aliphatichydrocarbons), hexane (n-hexane or mixture of linear and branched C₆acyclic aliphatic hydrocarbons), heptane (n-heptane or mixture of linearand branched C₇ acyclic aliphatic hydrocarbons), octane (n-octane or amixture of linear and branched C₈ acyclic aliphatic hydrocarbons), andcombinations thereof; alternatively, pentane (n-pentane or a mixture oflinear and branched C₅ acyclic aliphatic hydrocarbons), hexane (n-hexaneor mixture of linear and branched C₆ acyclic aliphatic hydrocarbons),heptane (n-heptane or mixture of linear and branched C₇ acyclicaliphatic hydrocarbons), octane (n-octane or a mixture of linear andbranched C₈ acyclic aliphatic hydrocarbons), and combinations thereof;hexane (n-hexane or a mixture of linear and branched C₆ acyclicaliphatic hydrocarbons), heptane (n-heptane or mixture of linear andbranched C₇ acyclic aliphatic hydrocarbons), octane (n-octane or amixture of linear and branched C₈ acyclic aliphatic hydrocarbons), andcombinations thereof; alternatively, pentane (n-pentane or a mixture oflinear and branched C₅ acyclic aliphatic hydrocarbons); alternatively,hexane (n-hexane or mixture of linear and branched C₆ acyclic aliphatichydrocarbons); alternatively, heptane (n-heptane or mixture of linearand branched C₇ acyclic aliphatic hydrocarbons); or alternatively,octane (n-octane or a mixture of linear and branched C₈ acyclicaliphatic hydrocarbons).

Non-limiting examples of suitable cyclic aliphatic hydrocarbon solventsinclude cyclohexane, methyl cyclohexane, and combinations thereof;alternatively cyclohexane; or alternatively, methylcyclohexane.

Oligomer Products and Polyalphaolefins

Embodiments of the present invention also are directed to oligomerproducts produced from a monomer comprising an olefin. For instance, thepresent invention encompasses any oligomer product produced by a processcomprising (i) introducing a monomer comprising an olefin and achemically-treated solid oxide into a reaction zone, and (ii)oligomerizing the monomer to form the oligomer product in the reactionzone. Features and characteristics of the monomer comprising the olefinand of the chemically-treated solid oxide are described herein.

It is contemplated that the oligomerization processes disclosed hereinhave excellent olefin conversions and selectivity to desired oligomerproduct fractions, such as dimers and/or trimers. In one embodiment, forexample, the monomer can comprise propylene, and the oligomer productcan be characterized by a total trimer/tetramer content of at least 70wt. %, at least 75 wt. %, at least 80 wt. %, from 70 to 95 wt. %, orfrom 70 to 90 wt. %. Additionally or alternatively, this oligomerproduct can be characterized by at least 30 wt. %, at least 40 wt. %, atleast 45 wt. %, from 35 to 60 wt. %, or from 40 to 55 wt. % trimers.Additionally or alternatively, this oligomer product can becharacterized by a weight ratio of trimers to tetramers in the oligomerproduct of greater than 1:1, e.g., a trimer:tetramer weight ratio in arange from 1.05:1 to 1.6:1, or from 1.1:1 to 1.5:1.

In another embodiment, the monomer can comprise 1-butene, 1-pentene,1-hexene, or any combination thereof, and the oligomer product can becharacterized by a total dimer/trimer content of at least 70 wt. %, atleast 80 wt. %, at least 85 wt. %, from 70 to 98 wt. %, or from 75 to 97wt. %. Additionally or alternatively, this oligomer product can becharacterized by at least 30 wt. %, at least 40 wt. %, at least 45 wt.%, from 35 to 65 wt. %, or from 40 to 65 wt. % trimers. Additionally oralternatively, this oligomer product can be characterized by a weightratio of trimers to dimers in the oligomer product of in a range from0.5:1 to 2:1, or a weight ratio greater than 1:1, e.g., a trimer:dimerweight ratio in a range from 1.02:1 to 2:1, or from 1.05:1 to 2:1.

In another embodiment, the monomer can comprise a C₈ to C₁₂ olefin(e.g., 1-octene, 1-decene, 1-dodecene, or any combination thereof), andthe oligomer product can be characterized by a dimer content of at least30 wt. %, at least 55 wt. %, at least 60 wt. %, from 30 to 98 wt. %,from 55 to 95 wt. %, or from 60 to 88 wt. %. Additionally oralternatively, this oligomer product can be characterized by a weightratio of dimers to trimers in the oligomer product of greater than 1:1,greater than 1.5:1, or greater than 2:1, e.g., a dimer:trimer weightratio in a range from 1.5:1 to 8:1, from 1.5:1 to 6:1, from 1.5:1 to4:1, from 2:1 to 8:1, from 2:1 to 6:1, or from 2:1 to 4:1.

In an embodiment of this invention, the oligomer product (alternatively,dimers; alternatively, trimers; alternatively, tetramers; oralternatively, any fraction comprising all or any portion of theoligomer product) can be isolated, e.g., from the reactor effluent ofthe oligomerization process. For instance, any process disclosed hereincan further comprise a step of removing a reactor effluent from thereaction zone, and separating at least a portion of thechemically-treated solid oxide from the reactor effluent. Additionallyor alternatively, any process disclosed herein can further comprise astep of removing at least a portion of the monomer from the reactoreffluent. As would be recognized by one of skill in the art, these stepscan be performed using any suitable technique, such as filtration,evaporation, or distillation, as well as combinations of two or more ofthese techniques.

The processes disclosed herein can further comprise a step of isolatingone or more fractions comprising all or a portion of the oligomerproduct. For instance and not limited thereto, a dimer fraction can beisolated, a trimer fraction can be isolated, a dimer and trimer fractioncan be isolated, a trimer and tetramer fraction can be isolated, atrimer and heavier oligomer fraction can be isolated, and so forth. Thisisolation step can be performed using any suitable technique, such asfiltration, evaporation, or distillation, as well as combinations of twoor more of these techniques, and these techniques can be performed atatmospheric or any suitable sub-atmospheric pressure.

Further, the oligomer product (alternatively, dimers; alternatively,trimers; alternatively, tetramers; or alternatively, any fractioncomprising all or any portion of the oligomer product) can behydrogenated. Thus, any of the processes described herein optionally canfurther comprise a step of hydrogenating the oligomer product(alternatively, dimers; alternatively, trimers; alternatively,tetramers; or alternatively, any fraction comprising all or any portionof the oligomer product). Suitable hydrogenation procedures andassociated metal catalysts (e.g., platinum, rhenium, palladium, nickel,etc.) are well known to those of skill in the art. Alternatively, theoligomer product (or a large fraction thereof) can be hydrogenatedfirst, and then isolated into one or more fractions, e.g., ahydrogenated dimer fraction, a hydrogenated trimer fraction, ahydrogenated dimer and trimer fraction, a hydrogenated trimer andtetramer fraction, a hydrogenated trimer and heavier oligomer fraction,and the like. The hydrogenated oligomer product, any hydrogenatedoligomer product fraction, or any fraction of the hydrogenated oligomerproduct, can be referred to as a polyalphaolefin.

Embodiments of the present invention also are directed to and encompassany oligomer product (alternatively, dimers; alternatively, trimers;alternatively, tetramers; or alternatively, any fraction comprising allor any portion of the oligomer product) or any polyalphaolefin producedby any of the processes disclosed herein. The oligomer product and thepolyalphaolefin can have any suitable kinematic viscosity at 100° C.,for instance, ranging from 1.8 to 12 cSt, from 1.8 to 10.4 cSt, from 1.8to 8.4 cSt, from 1.8 to 6.4 cSt, or from 1.8 to 4.4 cSt. Accordingly,fractions comprising all or any portion of the oligomer product and allor any portion of the polyalphaolefin can have a kinematic viscosity at100° C. that generally can fall within a range from 1.8 cSt to 2.2 cSt,from 2.3 cSt to 2.7 cSt, from 2.6 cSt to 3.4 cSt, from 3.6 cSt to 4.4cSt, from 4.6 cSt to 5.4 cSt, from 5.6 cSt to 6.4 cSt, from 6.6 cSt to7.4 cSt, from 7.6 cSt to 8.4 cSt, from 8.6 cSt to 9.4 cSt, or from 9.6cSt to 10.4 cSt, as well as combination thereof.

This invention also contemplates and encompasses any compositions (e.g.,lubricant compositions or lubricant formulations) or base oils thatcomprise the oligomer products (alternatively, dimers; alternatively,trimers; alternatively, tetramers; or alternatively, any fractioncomprising all or any portion of the oligomer products) orpolyalphaolefins produced or described herein.

An illustrative and non-limiting example of a polyalphaolefin of thepresent invention can comprise at least 80 wt. % hydrogenated oligomersof a C₆ to C₁₂ alpha olefin (or any other alpha olefin, any alpha olefinrange, or mixture of alpha olefins described herein, such as one or moreC₆ to C₁₂ alpha olefins, or one or more C₆ to C₁₂ normal alpha olefins),and the polyalphaolefin can be characterized by a viscosity indexgreater than or equal to 110 and a kinematic viscosity at −40° C. ofless than or equal to 1750 cSt. The polyalphaolefin can further comprisehydrogenated dimers and trimers at any suitable weight ratio ofhydrogenated dimers:trimers, for instance, greater than 2:1;alternatively, greater than 2.5:1; alternatively, greater than 3:1;alternatively, from 2:1 to 6:1; or alternatively, from 2.5:1 to 5:1.

Another illustrative and non-limiting example of a polyalphaolefin ofthe present invention can comprise at least 30 wt. % C₂₄ saturatedhydrocarbons (or at least 50 wt. %, or at least 75 wt. %, or at least 85wt. %), and the polyalphaolefin can be characterized by a viscosityindex greater than or equal to 110 and a kinematic viscosity at −40° C.of less than or equal to 1750 cSt. The polyalphaolefin can furthercomprise C₃₆ saturated hydrocarbons, and a weight ratio of C₂₄:C₃₆saturated hydrocarbons can be in any suitable range, such as greaterthan 2:1; alternatively, greater than 2.5:1; alternatively, greater than3:1; alternatively, from 2:1 to 6:1; or alternatively, from 2.5:1 to5:1. Moreover, another illustrative and non-limiting example of apolyalphaolefin of the present invention can comprise at least 30 wt. %C₂₀ saturated hydrocarbons (or at least 50 wt. %, or at least 75 wt. %,or at least 85 wt. %), and the polyalphaolefin can be characterized by aviscosity index greater than or equal to 110 and a kinematic viscosityat −40° C. of less than or equal to 1750 cSt. The polyalphaolefin canfurther comprise C₃₀ saturated hydrocarbons, and a weight ratio ofC₂₀:C₃₀ saturated hydrocarbons can be in any suitable range, such asgreater than 2:1; alternatively, greater than 2.5:1; alternatively,greater than 3:1; alternatively, from 2:1 to 6:1; or alternatively, from2.5:1 to 5:1.

These illustrative and non-limiting examples of polyalphaolefinsconsistent with the present invention also can have any of thecharacteristics or properties provided below, and in any combination.

In an embodiment, the polyalphaolefin can have a viscosity index in arange from 110 to 150. Other suitable non-limiting ranges for theviscosity index can include the following ranges: from 110 to 125, from110 to 120, from 112 to 150, from 112 to 125, or from 112 to 120. Otherappropriate ranges for the viscosity index of the polyalphaolefin arereadily apparent from this disclosure. The viscosity index is measuredin accordance with ASTM D7042-04.

In an embodiment, the polyalphaolefin can have a kinematic viscosity at−40° C. in a range from 1200 to 1750 cSt. Other suitable non-limitingranges for the kinematic viscosity at −40° C. can include the followingranges: from 1300 to 1750 cSt, from 1400 to 1750 cSt, from 1300 to 1700cSt, from 1400 to 1700 cSt, from 1350 to 1700 cSt, from 1350 to 1650cSt, or from 1350 to 1550 cSt. Other appropriate ranges for thekinematic viscosity at −40° C. of the polyalphaolefin are readilyapparent from this disclosure. Kinematic viscosities are measured inaccordance with ASTM D7042-04 (Stabinger Method).

In an embodiment, the polyalphaolefin can have a kinematic viscosity at40° C. in a range from 9 to 18 cSt. Other suitable non-limiting rangesfor the kinematic viscosity at 40° C. can include the following ranges:from 9 to 15 cSt, from 9 to 14 cSt, from 10 to 18 cSt, from 10 to 15cSt, from 11 to 18 cSt, from 11 to 15 cSt, or from 11 to 14 cSt. Otherappropriate ranges for the kinematic viscosity at 40° C. of thepolyalphaolefin are readily apparent from this disclosure.

In an embodiment, the polyalphaolefin can have a kinematic viscosity at100° C. in a range from 1.8 to 12 cSt. Other suitable non-limitingranges for the kinematic viscosity at 100° C. can include the followingranges: from 1.8 to 10.4 cSt, from 1.8 to 8.4 cSt, from 1.8 to 6.4 cSt,from 1.8 to 4.4 cSt, from 2.5 to 6.4 cSt, from 2.5 to 4.4 cSt, or from 3to 4.4 cSt. Other appropriate ranges for the kinematic viscosity at 100°C. of the polyalphaolefin are readily apparent from this disclosure.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Chemically-Treated Solid Oxide Preparation

The chemically-treated solid oxides were prepared as follows. Forsulfated alumina, Alumina A from W.R. Grace, having a surface area ofabout 300 m²/g and a pore volume of about 1.2 mL/g, was used. Aftercalcining in a muffle furnace for 12 hours at 600° C., the alumina wasallowed to cool. Then, the calcined alumina was impregnated with asolution of sulfuric acid in methanol, such that 3 mL of methanol wereadded per gram of alumina. The methanol contained enough sulfuric acidto equal about 15% sulfate based on the weight of the sulfated alumina.This sulfate-impregnated alumina was then placed in a flat pan andallowed to dry under vacuum at approximately 110° C. for about 16 hours.To calcine the support, about 10 g of the powdered mixture were placedin a 1.75-inch quartz tube fitted with a sintered quartz disk at thebottom. While the powder was supported on the disk, dry air (dried bypassing through a 13× molecular sieve column) was blown upward throughthe disk at a rate of about 1.6 to 1.8 standard cubic feet per hour; drynitrogen can be substituted for dry air. An electric furnace around thequartz tube was then turned on and the temperature was raised at therate of about 400° C. per hour to the desired calcining temperature ofabout 600° C. (except Examples 6-9, which used different calciningtemperatures). At this calcining temperature, the powder was allowed tofluidize for about three hours in the dry air. Afterward, the sulfatedalumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere.

Silica-coated aluminas were prepared as follows. The same alumina(Alumina A) used in preparing sulfated alumina was first calcined atabout 600° C. for approximately 6 hours, cooled to ambient temperature,and then contacted with tetraethylorthosilicate in isopropanol to equal25 wt. % SiO₂. After drying, the silica-coated alumina was calcined at600° C. for 3 hours. Fluorided silica-coated alumina (7 wt. % F) wasprepared by impregnating the calcined silica-coated alumina with anammonium bifluoride solution in methanol, drying, and then calcining for3 hours at 600° C. in dry air. Afterward, the fluorided silica-coatedalumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere.

Fluorided-chlorided silica-coated aluminas (4 wt. % Cl+7 wt. % F) wereproduced by first calcining the silica-coated alumina at 600° C. for 3hours. The chloriding step involved injecting and vaporizing CCl₄ intoan air stream (typically, over a time period of less than about 5minutes) used to fluidize the silica-coated alumina during calcinationat a peak chloriding temperature of 500° C. (total duration of thecalcining operation was 4 hours). The fluoriding step involved injectingand vaporizing tetrafluoroethane into the air stream (typically, over atime period of less than about 5 minutes) used to fluidize the chloridedsilica-coated alumina during calcination at a peak fluoridingtemperature of 500° C. (total duration of the calcining operation was4.5 hours).

Olefin Oligomerizations

Gas chromatographic (GC) analyses were performed using a split injectionmethod on an HP 5890 gas chromatograph with a flame ionization detector(FID). Initial oven temperature was 100° C. for 2 minutes and increased8° C./min to 185° C., then 20° C./min to 290° C. for 6 minutes. Thecolumn was an HP-1 column, 12 m×0.2 mm×0.33 μm. Data analysis wasperformed using Chemstation® software.

Examples 1-5

Oligomerization of 1-Dodecene with Sulfated Alumina at DifferentReaction Temperatures and Times

Examples 1-4 were conducted as follows. In an inert atmosphere drybox, apreviously dried 50 mL 3-necked round-bottom flask was charged with0.503 grams of sulfated alumina and a magnetic stir bar. The necks ofthe round-bottom flask were then fitted with rubber septa andtransferred from the drybox to a fume hood. The round-bottom flask wasthen placed on a heating mantle on the top of a magnetic stirrer. One ofthe rubber septa was then equipped with a needle connected to a positivesource of nitrogen inflow and a thermocouple. A second rubber septa wasequipped with a needle connected to a bubbler so as to maintain anitrogen atmosphere within the round-bottom flask.

For Examples 1A-1C, the reaction was initiated by charging 20 mL (15.94g) of 1-dodecene, by syringe, into the round-bottom flask containing 0.5g of sulfated alumina. Stirring of the reaction was initiated and thereaction mixture was heated to 110° C. Liquid samples were then removedfrom the round-bottom flask, by syringe, at (1A) 38 minutes, (1B) 2hours, and (1C) 4.5 hours of reaction time. The contents of theround-bottom flask were then allowed to cool to room temperature and thestirring of the reaction mixture was terminated. The liquid samples werethen analyzed by gas chromatography to determine composition of thereaction mixture. Table I provides the compositional make-up of theliquid samples.

For Examples 2A-2C, the reaction was initiated by charging 20 mL (15.94g) of 1-dodecene, by syringe, into the round-bottom flask containing 0.5g of sulfated alumina. Stirring of the reaction was initiated and thereaction mixture was heated to 150° C. Liquid samples were then removedfrom the round-bottom flask, by syringe, at (2A) 34 minutes, (2B) 2hours and 43 minutes, and (2C) 4.5 hours of reaction time. The contentsof the round-bottom flask were then allowed to cool to room temperatureand the stirring of the reaction mixture was terminated. The liquidsamples were then analyzed by gas chromatography to determinecomposition of the reaction mixture. Table I provides the compositionalmake-up of the liquid samples.

For Examples 3A-3D, the reaction was initiated by charging 20 mL (15.94g) of 1-dodecene, by syringe, into the round-bottom flask containing 0.5g of sulfated alumina. Stirring of the reaction was initiated and thereaction mixture was heated to 200° C. Liquid samples were then removedfrom the round-bottom flask, by syringe, at (3A) 30 minutes (188° C.),(3B) 58 minutes (201° C.), (3C) 2 hours (201° C.), and (3D) 4 hours and12 minutes (206° C.) of reaction time. The contents of the round-bottomflask were then allowed to cool to room temperature and the stirring ofthe reaction mixture was terminated. The liquid samples were thenanalyzed by gas chromatography to determine composition of the reactionmixture. Table I provides the compositional make-up of the liquidsamples.

For Examples 4A-4C, the reaction was initiated by charging 20 mL (15.94g) of 1-dodecene, by syringe, into the round-bottom flask containing 0.5g of sulfated alumina. Stirring of the reaction was initiated and thereaction mixture was heated to 150° C. Liquid samples were then removedfrom the round-bottom flask, by syringe, at (4A) 49 minutes, (4B) 2hours, and (4C) 4 hours of reaction time. The contents of theround-bottom flask were then allowed to cool to room temperature and thestirring of the reaction mixture was terminated. The liquid samples werethen analyzed by gas chromatography to determine composition of thereaction mixture. Table I provides the compositional make-up of theliquid samples.

Example 5 was conducted as follows. A dry 3-necked round-bottom flaskequipped with a mechanical stirrer, a thermocouple, a nitrogen inlet,and a nitrogen outlet connected to a bubbler, was charged, undernitrogen atmosphere, with 500 mL of previously dried 1-dodecene. Thecontents of round-bottom flask were then heated, with stirring, to 100°C. A sample of 14.315 grams of sulfated alumina, which had been dried ina vacuum oven over night at 240° C., was quickly removed from the vacuumoven and charged to the round-bottom flask under a nitrogen atmosphere.The reaction mixture was then heated to 150° C. and stirred. Liquidsamples were then removed from the round-bottom flask, by syringe, at(5A) 58 minutes, (5B) 1 hour and 54 minutes, (5C) 3 hours and 3 minutes,and (5D) 4 hours and 13 minutes of reaction time. The contents of theround-bottom flask were then allowed to cool to room temperature and thestirring of the reaction mixture was terminated. The liquid samples werethen analyzed by gas chromatography to determine composition of thereaction mixture. Table I provides the compositional make-up of theliquid samples. The oligomer product of Example 5 had a 100° C., 40° C.,and −40° C. kinematic viscosities of 3.2 cSt, 12.7 cSt, and 1,445 cSt,respectively. The viscosity index of the oligomer product was 114. Thekinematic viscosity and viscosity index for the oligomer product ofExample 5 were determined using ASTM D7042-04.

In Table I, Examples 1-5 are summarized. The product compositions areshown in wt. %, dimer/trimer is the dimer:trimer ratio in the oligomerproduct, dimer yield is the percentage of the dimer in the oligomerproduct, and the calculated viscosity at 100° C. is provided in cSt. Thecalculated viscosity was determined using a proprietary program thatcorrelates oligomer distribution with kinematic viscosity to provide acalculated kinematic viscosity based on known oligomer distributions.

As shown in Table I, regardless of the reaction temperature, monomerconversion increased with reaction time for all of the examples, and theamount of dimer also increased with reaction time for all of theexamples. Dimer yield was unexpectedly high for all examples, with about63-81 wt. % of the oligomer product (excluding residual monomer) beingthe C₂₄ dimer. Moreover, the sulfated alumina catalyst had surprisinglyhigh selectivity to the dimer, with ratios of dimer:trimer generallyranging from 2.6:1 to 5.3:1.

Examples 6-9

Oligomerization of 1-Dodecene with Sulfated Alumina Calcined atDifferent Temperatures

Examples 6-9 were conducted using the method as described above forExamples 1-4 at a reaction temperature of 150° C., and the liquidsamples were then analyzed by gas chromatography to determinecomposition of the reaction mixture. Table II provides the compositionalmake-up of the liquid samples. The sulfated alumina was either (Example6) not calcined, (Example 7) calcined at 100° C., (Example 8) calcinedat 200° C., or (Example 9) calcined at 300° C. For Example 6, liquidsamples were removed, by syringe, at (6A) 15 minutes, (6B) 30 minutes,(6C) 1 hour, and (6D) 2 hours of reaction time. For Example 7, liquidsamples were removed, by syringe, at (7A) 15 minutes, (7B) 30 minutes,(7C) 1 hour, and (7D) 2 hours of reaction time. For Example 8, liquidsamples were removed, by syringe, at (8A) 15 minutes, (8B) 30 minutes,(8C) 1 hour, and (8D) 2 hours of reaction time. For Example 9, liquidsamples were removed, by syringe, at (9A) 15 minutes, (9B) 30 minutes,(9C) 1 hour, and (9D) 2 hours of reaction time.

In Table II, Examples 6-9 are summarized. The product compositions areshown in wt. %, dimer/trimer is the dimer:trimer ratio in the oligomerproduct, dimer yield is the percentage of the dimer in the oligomerproduct (excluding residual monomer), and the calculated viscosity at100° C. is provided in cSt. Regardless of the calcination temperature,monomer conversion increased with reaction time for all of the examples,and the amount of dimer also increased with reaction time for all of theexamples. Dimer yield was unexpectedly high for all examples, with about66-85 wt. % of the oligomer product (excluding residual monomer) beingthe C₂₄ dimer. Moreover, the sulfated alumina catalyst had surprisinglyhigh selectivity to the dimer regardless of calcination temperature,with ratios of dimer:trimer generally ranging from 2.6:1 to 6.9:1.

TABLE I Summary of Examples 1-5. Temp Composition Dimer/ Dimer Calc.Example Time (° C.) C₁₂ C₂₄ C₃₆ C₄₈ C₆₀ C₇₂ C₈₄ Trimer Yield Viscosity1A 0:38 110 55.9% 30.3% 9.4% 2.68% 0.98% 0.71% 0.00% 3.2 69% 3.18 1B2:00 110 40.6% 39.4% 13.2% 4.26% 1.47% 0.55% 0.47% 3.0 66% 3.27 1C 4:30110 28.5% 45.3% 17.4% 5.92% 1.86% 0.65% 0.38% 2.6 63% 3.35 2A 0:30 15054.5% 34.4% 7.8% 2.24% 0.67% 0.33% 4.4 76% 2.97 2B 2:43 150 33.7% 46.7%14.0% 3.91% 1.06% 0.43% 0.24% 3.3 70% 3.11 2C 4:30 150 25.8% 50.1% 17.5%4.82% 1.22% 0.38% 0.12% 2.9 68% 3.17 3A 0:30 188 72.5% 19.0% 5.9% 1.72%0.47% 0.17% 3.2 69% 3.12 3B 0:58 201 57.9% 32.3% 7.4% 1.82% 0.48% 0.15%4.4 77% 2.92 3C 2:00 201 41.8% 43.2% 11.4% 2.72% 0.65% 0.33% 3.8 74%2.98 3D 4:12 206 28.0% 49.0% 17.4% 4.28% 1.04% 0.23% 0.05% 2.8 68% 3.144A 0:49 150 77.4% 15.7% 5.0% 1.47% 0.39% 0.09% 3.1 69% 3.12 4B 2:00 15074.6% 19.1% 4.6% 1.29% 0.35% 0.09% 4.1 75% 2.92 4C 4:00 150 66.7% 26.0%5.5% 1.43% 0.34% 0.06% 4.8 78% 3.14 5A 0:58 150 50.7% 39.8% 7.5% 1.48%0.36% 0.13% 5.3 81% 5B 1:54 150 39.7% 46.2% 11.1% 2.35% 0.39% 0.17%0.14% 4.2 77% 5C 3:03 150 32.9% 49.1% 13.9% 3.20% 0.65% 0.29% 3.5 73% 5D4:13 150 29.1% 50.2% 15.8% 3.88% 0.81% 0.25% 3.2 71%

TABLE II Summary of Examples 6-9. Calcination Composition Dimer/ DimerCalc. Example Time Temp (° C.) C₁₂ C₂₄ C₃₆ C₄₈ C₆₀ C₇₂ C₈₄ Trimer YieldViscosity 6A 0:15 N/A 47.8% 39.7% 9.1% 2.45% 0.72% 0.28% 4.4 76% 2.91 6B0:30 N/A 42.9% 43.0% 10.5% 2.65% 0.59% 0.33% 4.1 75% 2.98 6C 1:00 N/A38.7% 45.4% 11.9% 3.00% 0.71% 0.27% 3.8 74% 2.99 6D 2:00 N/A 34.9% 47.5%13.2% 3.25% 0.78% 0.33% 3.6 73% 3.01 7A 0:15 100 48.7% 41.0% 8.1% 1.68%0.42% 0.12% 5.1 80% 2.80 7B 0:30 100 41.8% 45.0% 10.3% 2.22% 0.53% 0.12%4.4 77% 2.89 7C 1:00 100 32.9% 48.9% 13.9% 3.25% 0.73% 0.35% 3.5 73%2.99 7D 2:00 100 25.4% 50.6% 18.0% 4.65% 1.08% 0.28% 2.8 68% 3.14 8A0:15 200 59.5% 34.3% 4.9% 0.76% 0.24% 0.26% 6.9 85% 2.69 8B 0:30 20050.6% 40.4% 7.3% 1.46% 0.31% 0.03% 5.5 82% 2.71 8C 1:00 200 40.1% 46.2%10.7% 2.21% 0.44% 0.34% 4.3 77% 2.89 8D 2:00 200 30.3% 50.1% 14.9% 3.51%0.81% 0.40% 3.4 72% 3.04 9A 0:15 300 49.9% 39.4% 8.3% 1.83% 0.42% 0.13%4.7 79% 2.89 9B 0:30 300 41.5% 44.1% 11.0% 2.59% 0.64% 0.21% 4.0 75%2.95 9C 1:00 300 33.6% 47.5% 14.3% 3.51% 0.81% 0.26% 3.3 72% 3.04 9D2:00 300 25.3% 49.2% 18.7% 5.17% 1.33% 0.29% 2.6 66% 3.21

Examples 10-11

Polyalphaolefin Properties Resulting from the Oligomerization of1-Dodecene with Sulfated Alumina

Example 10 was produced as described above for Example 5. Afterfiltration to remove the sulfated alumina, the oligomer product ofExample 10 was subjected to standard distillation conditions capable ofseparating 1-dodecene from the oligomer product, and then the oligomerproduct was hydrogenated. Example 11 is a comparative commercial 2.5 cStPAO product produced from the oligomerization of 1-dodecene using aBF₃-based catalyst system. Table III compares the properties of Examples10-11.

Unexpectedly, the product of Example 10 had higher molecular weight (asreflected by the higher viscosity at 100° C.), than that of Example 11,but with a beneficial combination of a lower viscosity at −40° C. and ahigher viscosity index.

TABLE III Examples 10-11. Example 10 Example 11 Viscosity @ 100° C.(cSt) 3.2 2.4 Viscosity @ 40° C. (cSt) 12.7 8.3 Viscosity @ −40° C.(cSt) 1445 1811 Viscosity Index 114 109 Bromine Index 93 ~50

Examples 12-14

Oligomerization of 1-Dodecene with Different Chemically-Treated SolidOxides

In a drybox under an N₂ atmosphere, a 30 mL glass vial vessel wascharged with a chemically-treated solid oxide and 10 mL of pre-dried anddegassed 1-dodecene. The glass vial was sealed and the mixture wasstirred at 25° C., for a set period of time. The liquid phase wasseparated by filtration. A sample of the liquid phase was then analyzedby gas chromatography to determine composition of the reaction mixture.Table IV provides the reaction information for Examples 12-14 and thecompositional make-up of the liquid samples. Example 12 used sulfatedalumina (S-A), Example 13 used fluorided silica-coated alumina (F-SCA),and Example 14 used fluorided/chlorided silica-coated alumina(F/Cl-SCA).

As shown in Table IV, at a reaction temperature of 25° C., Examples13-14 (fluorided silica-coated alumina, fluorided/chloridedsilica-coated alumina) had significantly higher monomer conversions thanExample 12 (sulfated alumina), resulting in the production of from 30%to over 100% more oligomer product from 1-dodecene. Examples 13-14 alsohad surprisingly high selectivity to the dimer, with ratios ofdimer:trimer ranging from 2.2:1 to 2.5:1.

Examples 15-17

Oligomerization of 1-Hexene with Different Chemically-Treated SolidOxides

In a drybox under an N₂ atmosphere, a 30 mL glass vial vessel wascharged with a chemically-treated solid oxide and 15 mL of pre-dried anddegassed 1-hexene. The glass vial was sealed and the mixture was stirredat 51° C. for 1 hour. The liquid phase was separated by filtration andthe unreacted 1-hexene was then removed by rotoevaporation at roomtemperature. A sample of the rotoevaporated liquid phase was thenanalyzed by gas chromatography to determine the composition of thereaction mixture. Table V provides reaction information for Examples15-17 and the compositional make-up of the product samples. Example 15used sulfated alumina (S-A), Example 16 used fluorided silica-coatedalumina (F-SCA), and Example 17 used fluorided/chlorided silica-coatedalumina (F/Cl-SCA).

As shown in Table V, at a reaction temperature of 51° C., Examples 16-17(fluorided silica-coated alumina, fluorided/chlorided silica-coatedalumina) had significantly higher monomer conversions than Example 15(sulfated alumina), resulting in the production of 20% more oligomerproduct from 1-hexene. Examples 15-16 also had surprisingly highselectivity to the trimer, with ratios of trimer:dimer ranging from1.05:1 to 1.8:1, and ratios of trimer:tetramer ranging from 4.2:1 to7:1.

Examples 18-21

Oligomerization of Propylene with Different Chemically-Treated SolidOxides

A 4-L steel autoclave reactor was loaded with 1 g of the catalyst undera purging stream of N₂. The reactor was sealed and then charged with 2.7liters of propylene. The reactor was brought to the reaction temperatureand stirred for 1 hour. The reactor temperature was then lowered to 40°C., the reactor was vented and then opened, and the liquid product wascollected. Product samples were analyzed by gas chromatography todetermine the composition of the reaction mixture. Table VI providesreaction information for Examples 18-21 and the compositional make-up ofthe product samples. Example 18 used sulfated alumina (S-A), andExamples 19-21 used fluorided silica-coated alumina (F-SCA).

As shown in Table VI, Examples 19-21 (fluorided silica-coated alumina)had significantly higher monomer conversions than Example 18 (sulfatedalumina), resulting in the production of from 30% to 75% more oligomerproduct from propylene. Examples 19-21 also had unexpectedly hightrimer/tetramer yield, with about 82-83 wt. % of the oligomer product(excluding residual monomer) being C₉ or C₁₂. Moreover, the oligomerproducts of Examples 19-21 contained over 40 wt. % trimer, and a ratioof trimer:tetramer ranging from 1.2:1 to 1.3:1.

TABLE IV Summary of Examples 12-14. 1-dodecene Product CompositionCatalyst Catalyst 1-dodecene Temperature Reaction time conversion DimerTrimer Example Type (mg) (mL) (° C.) (hr) (wt. %) (wt. %) (wt. %) 12 S-A410 10 25 2 14.4 78.3 21.7 13 F-SCA 410 10 25 2 18.9 69.1 30.9 14F/C1-SCA 425 10 25 2.2 30.1 71.3 28.7

TABLE V Summary of Examples 15-17. 1-hexene Product Composition CatalystCatalyst 1-hexene Product conversion Dimer Trimer Tetramer Example Type(mg) (g) (g) (wt. %) (wt. %) (wt. %) (wt. %) 15 S-A 326 10.17 4.22 41.453.6 41.0 5.4 16 F-SCA 330 10.17 5.11 50.2 31.5 55.4 13.1 17 F/C1-SCA331 10.17 5.08 49.9 45.1 48.2 6.8

TABLE VI Summary of Examples 18-21. Reactor Catalyst Catalyst pressureTemperature Product Product Composition (wt. %) Example Type (g) (psig)(° C.) (g) C₆ C₉ C₁₂ C₁₅ C₁₈ C₂₁ C₂₄ 18 S-A 1 440 70 23 3.5 48.3 34.39.3 3.3 1.0 0.4 19 F-SCA 1 448 70 30 3.2 46.1 37.0 9.6 2.9 0.9 0.2 20F-SCA 1 445 70 31 2.5 44.6 38.1 10.3 3.3 0.9 0.3 21 F-SCA 1 500 80 403.0 47.1 35.7 9.9 3.1 0.9 0.2

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1

A process comprising:

(i) introducing a monomer comprising a C₃ to C₃₀ olefin and achemically-treated solid oxide into a reaction zone; and

(ii) oligomerizing the monomer to form an oligomer product in thereaction zone.

Embodiment 2

The process defined in embodiment 1, wherein the chemically-treatedsolid oxide comprises a solid oxide treated with an electron-withdrawinganion, e.g., any solid oxide and any electron-withdrawing aniondisclosed herein.

Embodiment 3

The process defined in embodiment 2, wherein (a) the solid oxidecomprises silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or anymixture thereof, and (b) the electron-withdrawing anion comprisessulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, phospho-tungstate, or any combinationthereof.

Embodiment 4

The process defined in embodiment 2 or 3, wherein the solid oxidecomprises silica, alumina, silica-alumina, silica-coated alumina, or amixture thereof.

Embodiment 5

The process defined in embodiment 2 or 3, wherein the solid oxidecomprises silica-coated alumina.

Embodiment 6

The process defined in any one of embodiments 2-5, wherein theelectron-withdrawing anion comprises sulfate, fluoride, chloride, or anycombination thereof.

Embodiment 7

The process defined in any one of embodiments 2-6, wherein theelectron-withdrawing anion comprises sulfate.

Embodiment 8

The process defined in any one of embodiments 2-6, wherein theelectron-withdrawing anion comprises fluoride, chloride, or both.

Embodiment 9

The process defined in embodiment 1 or 2, wherein the chemically-treatedsolid oxide comprises fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, fluorided-chlorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof.

Embodiment 10

The process defined in embodiment 1 or 2, wherein the chemically-treatedsolid oxide comprises fluorided alumina, sulfated alumina, fluoridedsilica-alumina, sulfated silica-alumina, fluorided silica-coatedalumina, fluorided-chlorided silica-coated alumina, sulfatedsilica-coated alumina, or any combination thereof.

Embodiment 11

The process defined in embodiment 1 or 2, wherein the chemically-treatedsolid oxide comprises fluorided silica-coated alumina.

Embodiment 12

The process defined in embodiment 1 or 2, wherein the chemically-treatedsolid oxide comprises fluorided-chlorided silica-coated alumina.

Embodiment 13

The process defined in any one of embodiments 2-12, wherein the weightpercentage of the electron-withdrawing anion, based on the weight of thechemically-treated solid oxide, is any suitable amount or in any rangeof weight percentages disclosed herein, e.g., from 1 to 20 wt. %, from 2to 15 wt. %, or from 3 to 12 wt. %.

Embodiment 14

The process defined in any one of the preceding embodiments, wherein thechemically-treated solid oxide comprises silica-coated aluminacomprising silica in any suitable amount or in any range of weightpercentages disclosed herein, e.g., from 10 to 80 wt. % silica, from 25to 48 wt. % silica, or from 20 to 45 wt. % silica, based on the weightof the silica-coated alumina.

Embodiment 15

The process defined in any one of the preceding embodiments, wherein theoligomerizing step is conducted in the substantially absence oforganoaluminum compounds, metallocene compounds, or combinationsthereof.

Embodiment 16

The process defined in any one of embodiments 1-15, wherein the monomercomprises any suitable amount of the C₃ to C₃₀ olefin or an amount ofthe C₃ to C₃₀ olefin in any range disclosed herein, e.g., at least 50wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least95 wt. %, from 50 to 100 wt. %, from 80 to 100 wt. %, or from 80 to 98wt. %.

Embodiment 17

The process defined in any one of embodiments 1-16, wherein the monomercomprises a C₃ to C₅ olefin, a C₆ to C₁₈ olefin, or a C₈ to C₁₂ olefin.

Embodiment 18

The process defined in any one of embodiments 1-16, wherein the monomercomprises a C₃ to C₃₀ alpha olefin, a C₃ to C₅ alpha olefin, a C₆ to C₁₈alpha olefin, or a C₈ to C₁₂ alpha olefin.

Embodiment 19

The process defined in any one of embodiments 1-16, wherein the monomercomprises a C₃ to C₃₀ normal alpha olefin, a C₃ to C₅ normal alphaolefin, a C₆ to C₁₈ normal alpha olefin, or a C₈ to C₁₂ normal alphaolefin.

Embodiment 20

The process defined in any one of embodiments 1-16, wherein the monomercomprises propylene; alternatively, 1-butene; or alternatively,1-pentene.

Embodiment 21

The process defined in any one of embodiments 1-16, wherein the monomercomprises 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, or any combination thereof; alternatively, 1-octene,1-decene, 1-dodecene, or any combination thereof; alternatively,1-hexene; alternatively, 1-octene; alternatively, 1-decene,alternatively, 1-dodecene; alternatively, 1-tetradecene; oralternatively, 1-hexadecene.

Embodiment 22

The process defined in any one of embodiments 1-21, wherein the oligomerproduct is formed at any suitable oligomerization temperature or at anoligomerization temperature in any range disclosed herein, e.g., from 0°C. to 250° C., from 15° C. to 225° C., or from 20° C. to 180° C.

Embodiment 23

The process defined in any one of embodiments 1-22, wherein the reactionzone comprises any suitable reactor or any reactor disclosed herein,e.g., a fixed bed reactor, a stirred tank reactor, a plug flow reactor,a tubular reactor, or any combination thereof.

Embodiment 24

The process defined in any one of embodiments 1-23, wherein a weightratio of the monomer (comprising the C₃ to C₃₀ olefin or any otherolefin described herein) to the chemically-treated solid oxide is in anysuitable range or in any range of weight ratios disclosed herein, e.g.,from 1:1 to 1000:1, or from 2:1 to 100:1.

Embodiment 25

The process defined in any one of embodiments 1-24, wherein the processis conducted in a fixed bed reactor, and wherein the monomer (comprisingthe C₃ to C₃₀ olefin or any other olefin described herein) and thechemically-treated solid oxide are contacted at any suitable WHSV or aWHSV in any range disclosed herein, e.g., from 0.05 to 5, from 0.1 to 3,or from 0.5 to 2.5.

Embodiment 26

The process defined in any one of embodiments 1-25, wherein a conversion(or single pass conversion) of the monomer (comprising the C₃ to C₃₀olefin or any other olefin described herein) to the oligomer product isany suitable conversion (or single pass conversion) or in any range ofconversions (or single pass conversions) disclosed herein, e.g., from 10to 95 wt. %, from 20 to 90 wt. %, from 30 to 85 wt. %, from 40 to 80 wt.%, from 40 to 75 wt. %, or from 15 to 75 wt. %.

Embodiment 27

The process defined in any one of embodiments 1-26, wherein the monomercomprises propylene, and wherein the oligomer product comprises at least40 wt. % trimers and/or a weight ratio of trimers to tetramers in theoligomer product is greater than 1:1, e.g., from 1.05:1 to 1.6:1.

Embodiment 28

The process defined in any one of embodiments 1-26, wherein the monomercomprises 1-butene, 1-pentene, 1-hexene, or any combination thereof, andwherein the oligomer product comprises at least 40 wt. % trimers and/ora weight ratio of trimers to dimers in the oligomer product is greaterthan 1:1, e.g., from 1.02:1 to 2:1.

Embodiment 29

The process defined in any one of embodiments 1-26, wherein the monomercomprises any C₈ to C₁₂ olefin described herein (e.g., 1-octene,1-decene, 1-dodecene, or any combination thereof), and wherein theoligomer product comprises at least 30 wt. % dimers and/or a weightratio of dimers to trimers in the oligomer product is greater than0.5:1, e.g., greater than 1:1, from 0.5:1 to 6:1, or from 2:1 to 8:1.

Embodiment 30

The process defined in any one of embodiments 1-26, wherein the monomercomprises 1-dodecene, and wherein the oligomer product comprises from 30to 98 wt. % dimers and/or a weight ratio of dimers to trimers in theoligomer product is from 2:1 to 6:1.

Embodiment 31

The process defined in any one of embodiments 1-26, wherein the monomercomprises 1-dodecene, and wherein the oligomer product comprises from 55to 95 wt. % dimers and/or a weight ratio of dimers to trimers in theoligomer product is from 1.5:1 to 8:1.

Embodiment 32

The process defined in any one of embodiments 1-31, wherein thechemically-treated solid oxide comprises fluorided silica-coatedalumina, and wherein a conversion (or single pass conversion) of themonomer (comprising the C₃ to C₃₀ olefin or any other olefin describedherein) to the oligomer product is greater than that of a comparableprocess using sulfated alumina (instead of fluorided silica-coatedalumina), under the same oligomerization conditions.

Embodiment 33

The process defined in any one of embodiments 1-31, wherein thechemically-treated solid oxide comprises fluorided-chloridedsilica-coated alumina, and wherein a conversion (or single passconversion) of the monomer (comprising the C₃ to C₃₀ olefin or any otherolefin described herein) to the oligomer product is greater than that ofa comparable process using sulfated alumina (instead offluorided-chlorided silica-coated alumina), under the sameoligomerization conditions.

Embodiment 34

The process defined in any one of embodiments 1-33, wherein the processfurther comprises a step of removing a reactor effluent from thereaction zone and separating at least a portion of thechemically-treated solid oxide from the reactor effluent.

Embodiment 35

The process defined in embodiment 34, wherein the removing step isperformed using any suitable technique or any technique disclosedherein, e.g., filtration, evaporation, or distillation, as well ascombinations thereof.

Embodiment 36

The process defined in any one of embodiments 1-35, wherein the processfurther comprises a step of removing at least a portion of the monomerfrom the reactor effluent.

Embodiment 37

The process defined in any one of embodiments 1-36, wherein the processfurther comprises a step of isolating one or more fractions comprisingall or a portion of the oligomer product.

Embodiment 38

The process defined of embodiment 37, wherein the isolating step isperformed using any suitable technique or any technique disclosedherein, e.g., filtration, evaporation, or distillation, as well ascombinations thereof.

Embodiment 39

The process defined in any one of embodiments 37-38, wherein the processfurther comprises a step of hydrogenating at least one of the one ormore fractions comprising all or a portion of the oligomer product usingany suitable technique, or any technique disclosed herein, to form apolyalphaolefin.

Embodiment 40

An oligomer product (or fraction comprising all or a portion of theoligomer product) produced by the process defined in any one ofembodiments 1-38.

Embodiment 41

A polyalphaolefin produced by the process defined in embodiment 39.

Embodiment 42

A composition comprising the oligomer product (or fraction comprisingall or a portion of the oligomer product) defined in embodiment 40 orthe polyalphaolefin defined in embodiment 41.

Embodiment 43

A base oil or lubricant composition comprising the oligomer product (orfraction comprising all or a portion of the oligomer product) defined inembodiment 40 or the polyalphaolefin defined in embodiment 41.

Embodiment 44

A polyalphaolefin comprising (at least 80 wt. %) hydrogenated oligomersof a C₆ to C₁₂ olefin (or any other C₆ to C₁₂ olefin described herein),wherein the polyalphaolefin has a viscosity index greater than or equalto 110 and a kinematic viscosity at −40° C. of less than or equal to1750 cSt.

Embodiment 45

The polyalphaolefin defined in embodiment 44, wherein thepolyalphaolefin further comprises hydrogenated dimers and trimers, andhaving any weight ratio of hydrogenated dimers:trimers greater than orequal to 2:1 described herein, e.g., from 2:1 to 6:1.

Embodiment 46

A polyalphaolefin comprising at least 30 wt. % C₂₄ saturatedhydrocarbons, wherein the polyalphaolefin has a viscosity index greaterthan or equal to 110 and a kinematic viscosity at −40° C. of less thanor equal to 1750 cSt.

Embodiment 47

The process defined in embodiment 46, wherein the polyalphaolefinfurther comprises C₃₆ saturated hydrocarbons, and a weight ratio ofC₂₄:C₃₆ saturated hydrocarbons is greater than or equal to 2:1, e.g.,from 2:1 to 6:1.

Embodiment 48

The polyalphaolefin defined in any one of embodiments 44-47, wherein thepolyalphaolefin has a viscosity index in a range from 110 to 125.

Embodiment 49

The polyalphaolefin defined in any one of embodiments 44-48, wherein thepolyalphaolefin has a kinematic viscosity at −40° C. in a range from1300 to 1700 cSt.

Embodiment 50

The polyalphaolefin defined in any one of embodiments 44-49, wherein thepolyalphaolefin has a kinematic viscosity at 40° C. in a range from 9 to15 cSt.

Embodiment 51

The polyalphaolefin defined in any one of embodiments 44-50, wherein thepolyalphaolefin has a kinematic viscosity at 100° C. in a range from 1.8to 12 cSt.

We claim:
 1. A polyalphaolefin comprising hydrogenated dimers andtrimers of 1-dodecene, wherein the polyalphaolefin has: a viscosityindex greater than or equal to 110; a kinematic viscosity at −40° C. ofless than or equal to 1750 cSt; and a weight ratio of C₂₄:C₃₆ saturatedhydrocarbons in a range from 2:1 to 6:1.
 2. The polyalphaolefin of claim1, wherein: the viscosity index is in a range from 110 to 125; and thekinematic viscosity at −40° C. is in a range from 1300 to 1700 cSt. 3.The polyalphaolefin of claim 2, wherein the polyalphaolefin comprises atleast 50 wt. % C₂₄ saturated hydrocarbons and the polyalphaolefin has akinematic viscosity at 40° C. in a range from 9 to 18 cSt.
 4. Thepolyalphaolefin of claim 1, wherein: the viscosity index is in a rangefrom 110 to 150; and the kinematic viscosity at −40° C. is in a rangefrom 1200 to 1750 cSt.
 5. The polyalphaolefin of claim 4, wherein thepolyalphaolefin comprises at least 75 wt. % C₂₄ saturated hydrocarbonsand has a kinematic viscosity at 100° C. in a range from 1.8 to 12 cSt.6. The polyalphaolefin of claim 1, wherein: the viscosity index is in arange from 112 to 150; and the kinematic viscosity at −40° C. is in arange from 1350 to 1650 cSt.
 7. The polyalphaolefin of claim 6, whereinthe polyalphaolefin comprises at least 85 wt. % C₂₄ saturatedhydrocarbons and has a kinematic viscosity at 100° C. in a range from1.8 to 10.4 cSt.
 8. A polyalphaolefin comprising hydrogenated dimers andtrimers of 1-decene, wherein the polyalphaolefin has: a viscosity indexgreater than or equal to 110; a kinematic viscosity at −40° C. of lessthan or equal to 1750 cSt; and a weight ratio of C₂₀:C₃₀ saturatedhydrocarbons of greater than 2:1.
 9. The polyalphaolefin of claim 8,wherein: the viscosity index is in a range from 110 to 125; and thekinematic viscosity at −40° C. is in a range from 1300 to 1700 cSt. 10.The polyalphaolefin of claim 9, wherein the polyalphaolefin comprises atleast 50 wt. % C₂₀ saturated hydrocarbons and the polyalphaolefin has akinematic viscosity at 40° C. in a range from 9 to 18 cSt.
 11. Thepolyalphaolefin of claim 8, wherein the polyalphaolefin comprises atleast 75 wt. % C₂₀ saturated hydrocarbons and has a kinematic viscosityat 100° C. in a range from 1.8 to 12 cSt.
 12. The polyalphaolefin ofclaim 11, wherein: the viscosity index is in a range from 110 to 150;the kinematic viscosity at −40° C. is in a range from 1200 to 1750 cSt;and the weight ratio of C₂₀:C₃₀ saturated hydrocarbons is in a rangefrom 2.5:1 to 5:1.
 13. The polyalphaolefin of claim 8, wherein: theviscosity index is in a range from 112 to 150; the kinematic viscosityat −40° C. is in a range from 1350 to 1650 cSt; and the weight ratio ofC₂₀:C₃₀ saturated hydrocarbons is greater than 3:1.
 14. Thepolyalphaolefin of claim 13, wherein the polyalphaolefin comprises atleast 85 wt. % C₂₀ saturated hydrocarbons and has a kinematic viscosityat 100° C. in a range from 1.8 to 10.4 cSt.